EP1564208B1

EP1564208B1 - Process for producing methionine

Info

Publication number: EP1564208B1
Application number: EP04003353A
Authority: EP
Inventors: Dr.Dieter Buss; Dr. Ron Stockfleth; Martin Körfer; Dr. Jürgen Stock; Dr. Ralf Goedecke; Dr. Hans-Joachim Hasselbach; Gundolf Hornung
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2004-02-14
Filing date: 2004-02-14
Publication date: 2011-05-18
Anticipated expiration: 2024-02-14
Also published as: JP4939758B2; CN1680311A; EP1564208A1; BRPI0500394A; KR20060041832A; US20050267314A1; SG119263A1; ATE509908T1; KR101149143B1; RU2382768C2; RU2005103732A; JP2005225882A; ES2365849T3; US7119228B2; CN100410238C

Abstract

The invention refers to an improved process for producing methionine where the by-product methionyl-methionine is quickly converted to the product methionine by a hydrolysis reaction. The invention is characterized in that the reaction is performed at high temperatures (200 DEG C to 280 DEG C) and short residence times (20 s bis 200 s). The process is suited to increase the final yield of the desired end product methionine during a process for producing methionine. <??>Because of the higher temperatures significantly higher space-time yields can be achieved, whereby the economic efficiency of the process described by this invention can be guaranteed.

Description

Field of the Invention

The present invention refers to a process to quickly hydrolyze the dipeptide methionyl-methionine. The hydrolysis reaction might be carried out in connection with a process for producing methionine for increasing the final yield of the desired end product methionine.

Background of the Invention

Processes for producing methionine are well known in the art and are for example described in US 4,069,251 . During processes for producing methionine, one of the most prominent side products is the dipeptide methionyl-methionine. For optimizing the yield of the methionine forming reaction, one might benefit from the hydrolysis of this dipeptide. That is, due the cleavage of methionyl-methionine, resulting in two methionine molecules, a higher yield of the final product can be obtained.
The hydrolysis or dipeptide cleavage reaction is, however, subject to various imponderabilities. One has to bear in mind that during the hydrolysis by-products might be formed. The by-products may interfere negatively with the carbonization reaction taking place during the final step of methionine formation by crystallization at lower pH values.
The prior art EP 839 804 suggests to hydrolyze methionine dimers at temperatures within a range of 150 to 200°C, preferably at 170°C to 190°C. It is stated that at temperatures above 200°C the resulting methionine might suffer from thermal degradation and that still further materials of the reaction equipment corrode at temperatures above 200°C.
According to EP 1 312 611 , proteins are degraded to peptides and/or amino acids in supercritical water (that is above 355°C with a pressure of at least 22 MPa) or highpressure hot water near the critical point. However, at such high temperatures, highly corrosion resistant and hence extremely expensive equipment would become necessary. Furthermore, undesired side reactions and resulting by-products are expected to occur at such high temperatures. Still further, the end product methionine will be subject to thermal degradation.
The dipeptide cleavage, i.e. the hydrolysis of methionyl-methionine, typically occurs slowly at temperatures below 200°C, hence such temperature ranges would seem unsuitable for industrially applicable processes since the hydrolysis takes too long from an economic point of view. On the other hand, supercritical water presents the above-mentioned drawbacks, due to increased side reactions and the risk of thermal degradation of the desired end product methionine.
Thus, there is a strong need to provide an economically viable process for hydrolyzing methionyl-methionine at reasonable rates, while undesired side reactions and the degradation of the end product are avoided. Simultaneously, the facilities consisting of highly corrosion-resistant and thus expensive materials should be kept small.

Summary of the Invention

It has now surprisingly been found that the hydrolysis of methionyl-methionine can be carried out with significantly higher space-time yields (i.e. at low reaction volumes) by a process as set out in the claims.
According to the present invention, there is provided a process for producing methionine which comprises the steps of:

a) adding at least one compound selected from potassium carbonate, potassium bicarbonate and potassium hydroxide to a solution containing 5- (β-methylmercaptoethyl)hydantoin to hydrolyze the 5- (β-methylmercaptoethyl)hydantoin to obtain a solution containing methionine,
b) saturating the solution containing methionine with carbon dioxide to precipitate the methionine, and separating the precipitated methionine while leaving a first filtrate behind,
c) dividing the first filtrate into a first part and a second part returning the first part to step (a), and transferring the second part to step (d), wherein the first part of the first filtrate can be absent,
d) heating the second part of the first filtrate to a temperature from 210°C to 280°C for a residence time between 20 and 200 seconds and at a pressure above the vapor pressure of the water at the temperature employed, and saturating the heat-treated filtrate with carbon dioxide to precipitate the methionine and potassium bicarbonate, and separating the precipitated methionine and potassium bicarbonate while leaving a second filtrate behind, and
e) discharging the second filtrate or returning it to step (a).

According to the improved process of the present invention, significantly higher space-time yields can be achieved, whereby the economic efficiency of the process can be guaranteed.

Detailed Description of the Invention

The present invention is to be applied to a process for producing methionine which comprises hydrolyzing 5- (β-methylmercaptoethyl)hydantoin by using at least one member selected from potassium carbonate, potassium bicarbonate and potassium hydroxide, then precipitating methionine out of the reaction liquid under applied pressure of carbon dioxide, separating and collecting the methionine to leave a filtrate, and recycling, for reusing, the filtrate to the step of the hydrolysis of the hydantoin compound.
In the present invention, the conditions for the above-mentioned steps (a) and (b) are not particularly limited. As to the conditions for steps (a) and (b), known methods, for example as described in U.S. Pat. No. 4,069,251 and U.S. Pat. No. 4,303,621 , can be used. In such a method, 5-(β-methylmercaptoethyl)hydantoin is hydrolyzed by using potassium carbonate and/or potassium bicarbonate, the ratio between the hydantoin and the alkali (potassium carbonate and/or potassium bicarbonate) possibly being between 1:1 and 1:5, at an approximate temperature of from 120°C to 220°C, then carbon dioxide is fed to the reaction system to saturate the methionine-containing solution and thereby to precipitate methionine, and the methionine thus precipitated is separated by conventional methods of solid-liquid separation.
In the present invention, part of the first filtrate left behind in step (b) can be returned to the circulatory system as it is or after it is concentrated, and recycled to and reused in step (a). Recycling and reusing all the filtrate in this way over a long period would undesirably accumulate impurities and decomposition products in the system, which would reduce the purity of methionine produced. Therefore, in order to avoid the potential risk of accumulation of impurities and colored components in the system, it has been recommended to remove the filtrate according to necessity, for example in a definite proportion, out of the system (the so-called partial purging).
In the present invention, the second filtrate left behind in step (d) can be returned to step (a), although it can be discharged economically and environmental-friendly.
In the present invention, the amount of the filtrate to be partly purged (second part of the first filtrate in step (c)) is not particularly limited and may vary depending on the amounts of impurities and colored substances contained in the first filtrate, but it is preferably about 3-20%, more preferably 3-10% of the total amount of the first part of the first filtrate if it is present and the second filtrate if it is recycled and reused. The second part of the first filtrate can be heat-treated as it is or after it is concentrated. The filtrate to be heat-treated usually contains about 90-160 g/l of potassium, about 30-100 g/l of methionine and about 5-60 g/l of methionyl-methionine. The concentration of potassium referred to in the present invention may be determined by titration.
The temperature of the heat treatment (step (d)) of the second part of the first filtrate is particularly critical and falls within a range of 210°C-280°C, preferably within an range of 220°C-280°C, more preferably of from 220°C-260°C. The dimer can be rapidly hydrolyzed at a temperature higher than 200°C, for a time period short enough to prevent the thermal degradation of methionine.
The period of time for heat treatment also is particularly critical and may vary depending an the concentration of methionine dimer in the second part of the first filtrate. It is within a range of 20 s to 200 s, preferably within a range of 20 s to 150 s, more preferably within a range of 20 s to 100 s, and most preferably within a range of 20 s to 60 s. With longer periods of time of heat treatment the methionine would suffer thermal degradation.
It should further be noted, that step (d) should be carried out at a pressure above the vapor pressure of the water at the temperature employed.
The pressure of carbon dioxide gas to be applied, in terms of gauge pressure (the amount by which the total absolute pressure exceeds the ambient atmospheric pressure), is not critical, but usually ranges from about 1.5-20 bar, preferably about 2-6 bar. When the pressure of carbon dioxide gas is less than about 1.5 bar the recoveries of methionine and potassium bicarbonate tend to be insufficient; on the other hand, even when the pressure is increased over about 20 bar, sometimes no further improvement in these recoveries is observed.
The precipitation is preferably carried out at low temperatures. The precipitation temperature, particularly at the time of completion of the precipitation, preferably falls within the range of from about -10°C to about +40°C, more preferably from about 0°C to about +20°C, still more preferably in the neighborhood of about 0°C to about +5°C.
In the present invention, a concentrating operation can be conducted in any step, and is preferably conducted before and/or after the heat treatment of the second part of the first filtrate. The conditions of the concentrating operation are not particularly limited so long as they do not cause substantial thermal degradation of methionine, therefore, various conditions may be adopted in principle. However, in consideration of the energy efficiency and the corrosion of the materials of the reaction equipment, the temperature of the concentrating operation preferably falls within the range of from about 50°C to about 160°C, more preferably from about 50°C to about 140°C, and the pressure of the concentrating operation preferably falls within the range of from 0 to about 2 bar in terms of absolute pressure or a lower pressure, more preferably from 0 to about 1.5 bar in terms of absolute pressure.
In the present invention, the concentrating operation can be conducted simultaneously in combination with the heat-treating operation in step (d). In such a case, the concentrating operation would naturally be conducted under the claimed operation conditions of heat treatment, i.e., above 200°C for a time period of less than 200 s. However, it would not be preferable from the viewpoint of energy efficiency and other factors to adopt the relatively severe operation conditions in heat treatment for the purpose of concentrating operation. Therefore, the concentrating operation and the heat-treating operation are preferably conducted independently of each other.
According to the present invention, treating the second part of the first filtrate in the manner described above enables to remove the impurities and colored components present in the circulatory system to the outside of the system while effectively recovering methionine and potassium bicarbonate contained in the filtrate.
Step (d) of treating second part of the first filtrate in the present invention can be conducted either batchwise or continuously.
As described above, according to the present invention, merely by using a method which comprises heat-treating the second part of the first filtrate taken from the conventional process for producing methionine, and precipitating methionine out of the heat-treated filtrate under applied pressure of carbon dioxide gas, methionine dimer present in the system can be utilized effectively and resultantly the yield of methionine is improved, the accumulation of impurities and colored substances in the reaction system is avoided, and methionine and potassium bicarbonate can be recovered easily and with good efficiency. Thus, the present invention is of a great industrial value.
The process according to the invention is suited to increase the yield of the final end product methionine during a process for producing methionine. Due to significantly shorter reaction times (residence times of from 20 s to 200 s) the facilities consisting of special materials, can be constructed smaller, making the process most economic.
It should be noted, that the hydrolysis (step (d)) of the present invention can be carried out without any addition of a solvent. Furthermore, the hydrolysis of the present invention can be carried out directly with the methionine-mother liquor as starting material. The reaction is catalyzed by either acid or base. Suitable catalyzation can be achieved by adding KOH to adjust the pH to values about 14. Within the claimed temperature and pressure ranges, there occur no bothering side products during the hydrolysis reaction in view of the final carbonization reaction.

Brief Description of the Figure

Figure 1 shows a flow chart of the laboratory facility for the embodiment shown in Example 1 below.

The present invention is described in detail below with reference to Examples.

Example 1

As to the description of Example 1, please refer also to Figure 1. In Figure 1 the used numbers have the following meanings:

101: glass container
102: HPLC pump
103: coiled tubing reactor
104: cryostat device
105: washing bottle

The reactant solution is suck from the glass container 101 by the HPLC pump 102. The volume flow is regulated by the number of rotations of the HPLC pump (FIC 102.1). The pressure at the pressure side of the pump is regulated by the pressure control valve (PIC S+ 102.2). An interlock (S+) stops the pump, if the pressure exceeds 40 MPa.
At the pressure side of the pump the starting mixture flows in a 3x1 mm capillary into the coiled tubing reactor 103. The coiled tubing reactor consists of 6 m capillary of 3x1 mm, wrapped up a tube with an outer diameter of 168 mm filled with isolation material. The capillary wrapped up this tube is incorporated in a heat sleeve with a nominal power of 2 kW. In the hot section between the wrapped capillary and the heat sleeve there are two thermocouples (TI 103.1 and 103.2), one of which serves as over-temperature safety device (TI S+ 103.2).
Downstream the reactor a T-piece can be found, in which a thermocouple is screwed in (TIC 103.3). Therewith the temperature of the solution at the outlet of the reactor 103 is measured. This measured value is the actual value of the temperature control. For control a further thermocouple (TI 103.4) can be found at the outlet of the reactor, which is fixed outside the capillary. Subsequently the capillary passes a cryostat device, thus the product solution is cooled to about 50°C.
The pressure of the whole facility is shown by the pressure gauge downstream the cryostat device (PI 104.1). The reactant solution is set free by the pressure control valve and collected by the empty washing bottle 105.
With the laboratory facility shown in Figure 1, a mother liquor with the composition 4.25 mass-% of methionine, 3.36 mass-% of methionyl-methionine and 17.8 mass-% of potassium achieved conversion rates of methionyl-methionine listed in Table 1. The conversion rate there is defined as: $conversion = \frac{{[met - met]}_{in} - {[met - met]}_{out}}{{[met - met]}_{in}} .$

Where [met - met] is the concentration of methionyl - methionine at the inlet and outlet of the laboratory facility, respectively.

Table 1

Conversion Rates achieved with Example 1
Temperature	Residence time	Conversion
[°C]	[s]	[%]
223	24	21
223	24	29
223	32	34
223	39	38
239	18	38
239	24	40
239	31	47
239	38	58
239	60	63
239	107	77
239	157	83
254	18	48
254	23	62
254	30	64
254	37	75

Claims

A process for producing methionine which comprises the steps of:
a) adding at least one compound selected from potassium carbonate, potassium bicarbonate and potassium hydroxide to a solution containing 5- (β-methylmercaptoethyl)hydantoin to hydrolyze the 5- (β-methylmercaptoethyl)hydantoin to obtain a solution containing methionine,

b) saturating the solution containing methionine with carbon dioxide to precipitate the methionine, and separating the precipitated methionine while leaving a first filtrate behind,

c) dividing the first filtrate into a first part and a second part returning the first part to step (a), and transferring the second part to step (d), wherein the first part of the first filtrate can be absent,

d) heating the second part of the first filtrate to a temperature from 210°C to 280°C for a residence time between 20 and 200 seconds and at a pressure above the vapor pressure of the water at the temperature employed, and saturating the heat-treated filtrate with carbon dioxide to precipitate the methionine and potassium bicarbonate, and separating the precipitated methionine and potassium bicarbonate while leaving a second filtrate behind, and

e) discharging the second filtrate or returning it to step (a).
Process according to claim 1, wherein the temperature is from 220°C to 280°C.
Process according to claims 1 to 2, wherein the temperature is from 220°C to 260°C.
Process according to any of the preceding claims, wherein the residence times are between 20 and 100 s.
Process according to any of the preceding claims, wherein the used starting material in step d) is the methionine-mother liquor.
Process according to any of the preceding claims, wherein step d) is carried out in the absence of a solvent.